CN1826710B - Corrosion resistant fuel cell terminal plates - Google Patents
Corrosion resistant fuel cell terminal plates Download PDFInfo
- Publication number
- CN1826710B CN1826710B CN2004800035927A CN200480003592A CN1826710B CN 1826710 B CN1826710 B CN 1826710B CN 2004800035927 A CN2004800035927 A CN 2004800035927A CN 200480003592 A CN200480003592 A CN 200480003592A CN 1826710 B CN1826710 B CN 1826710B
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- Prior art keywords
- end plaste
- conductive
- corrosion
- layer
- metal
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to an electrochemical cell having a terminal collector plate element that conducts electrical current from the stack. The terminal plate has an electrically conductive region and an electrically non-conductive region of the surface. The non-conductive region is coated with a corrosion resistant coating that comprises either a passivation layer, a corrosion-resistant polymeric layer, or both. Optionally, the conductive region of the terminal plate may be protected from oxidation, by coating with an oxidation-resistant metal layer. The oxidation-resistant layer maybe further coated with a conductive oxidation-resistant polymeric layer. Other preferred aspects of the present invention include methods of treating the terminal plate to resist corrosion and oxidation while still maintaining electrical conductivity.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells, more specifically relate to corrosion-resistant terminal collector plates and manufacture method thereof.
Background technology
Fuel cell is proposed as power supply and is used for electric motor car or other purposes.Wherein a kind of known fuel cell is PEM (being a proton exchange membrane) fuel cell, comprise so-called " membrane electrode assembly ", this membrane electrode assembly comprises thin solid polymer membrane electrolyte, and its anode is positioned at the electrolytical face of film and negative electrode is positioned at another relative face of film electrolyte.Anode and negative electrode typically comprise the carbon particulate of refinement division, the catalyst particles of the very refinement of adhering on the surfaces externally and internally of carbon particulate division and the proton conductive substance that mixes with catalyst and carbon particulate.
The membrane electrode assembly is clipped between the contact element of a pair of conduction as anode and cathode collector, and contact element can have suitable passage and opening, and distributing the gaseous reactant of fuel cell on the surface of anode and negative electrode respectively by this passage and opening (is H
2And O
2/ air).
The bipolar proton exchange membrane fuel cell comprises the in series membrane electrode assembly of stack up of a plurality of electricity, is not separated from each other there to be infiltrative conductive contact element between one and the next one, and this contact element is called bipolar plates or barrier film.Barrier film or bipolar plates have two working faces, and a working face is faced the anode of a battery, and another working face is in the face of the negative electrode of next battery adjacent in the battery pile, and each bipolar plates is conduction current between adjacent battery.Contact element in the battery pile end is called as end plate, end plaste or collector plate.These terminal collector contact with the conducting element that is clipped between terminal bipolar plate and the terminal collector plate serves.
As seen, terminal collector plate serves has multiple function, comprises the sealed cell heap, gives conductivity, allows the turnover of fluid and stable material is provided between battery pile and external environment condition.This type of function as much as possible is optimized, and cost cheap as far as possible be a challenge.
Summary of the invention
The invention provides the electrochemical cell stack with terminal collector end plate, this end plate has conductive region and non-conductive zone.Non-conductive zone comprises that at least one slit goes into or go out battery pile with communication of fluid.Non-conductive zone is coated with corrosion resistant protective coating.This coating comprises passivation layer, corrosion-resistant polymer coating, or comprise said two devices.
In another embodiment of the present invention, the conductive region of end plaste is coated with the protective layer of conduction, comprises the oxidation resistant metal layer of conduction.Oxidation resistant metal layer selectively further is coated with the oxidation resistant polymers coating of conduction.
Another aspect of the present invention comprises the processing method of end plaste, thinks that non-conductive zone provides corrosion-resistant protection.The aspect of processing method comprises the conductive region with the oxidation resistant polymers coating protection end plaste that contains electrically conductive particles further.
The further range of application of the present invention is clear with discussing in the detailed description later.It will be appreciated that detailed argumentation and specific example when showing the preferred embodiment of the present invention, its intention only is used for setting forth and being not used in the qualification scope of invention.
Description of drawings
The detailed description and the accompanying drawings will make that the understanding of the present invention is more abundant, wherein:
Fig. 1 is the schematic diagram of two batteries in the pem fuel cell stack of liquid cools;
Fig. 2 is a typical terminal collector end plate, has shown the preferred embodiments of the present invention; And
Fig. 3 is the sectional view along 3-3 ' line among Fig. 2, has shown the surface of the terminal collector end plate of the preferred embodiment of the present invention.
Embodiment
Being described in of following preferred embodiment only is exemplary and be not intended to limit the present invention and be suitable for and purposes in essence.
The present invention considers the terminal collector end plate (hereinafter being called " end plaste ") in the electrochemical fuel cell stack, it has adopted lightweight perishable electric conducting material, this electric conducting material has conduction region and non-conductive area, and wherein the non-conductive area is treated to corrosion-resistant and surface conductivity is minimized.Further, another aspect of the present invention is considered the conduction region of end plaste, and it scribbles the resistance to oxidation protective finish of conduction.At first for a better understanding of the present invention, description provided herein to typical fuel cell and heap.
Fig. 1 has described two independent proton exchange membrane (PEM) fuel cell, and they are connected to form the battery pile with a pair of membrane electrode assembly (MEA) 4 and 6, and the conduction bipolar separator plate 8 by liquid cools between the membrane electrode assembly is separated mutually.Be not connected on the demarcation strip 8 that the single fuel cell in the battery pile has the single electroactive side of band.In battery pile, preferred bipolar separator plate 8 has two electroactive sides 20,21 usually in battery pile, and therefore each electroactive side 20,21 is called as " bipolar " plate respectively towards the independent MEA 4,6 that separates, have opposite charges.As described here, fuel cell pack is described to have conductive bipolar plate, yet the present invention can be applicable to only have the battery pile of single fuel cell equally.
Oxygen supplies to the cathode side of fuel cell pack from storage box 46 by suitable service 42, and hydrogen supplies to the anode-side of fuel cell by suitable service 44 from storage box 48.Selectively, air can supply to cathode side from environment, and hydrogen supplies to anode-side from methyl alcohol or gasoline reform device etc.The H of MEA also is provided
2And O
2The discharge duct 41 of/air side.Other pipeline 50 is provided, has been used for from the memory block 52 through bipolar plates 8 and end plates 14,16 and leave discharge line 54 circulating coolants.
Equidistant bipolar plates exploded view (as sequence number 8) is shown in the U.S. Patent number 6,372,376 of authorizing people such as Fronk.Admit that as those skilled in the art bipolar plates can be used as single fuel cell conductive plate, it is boundary in inside with MEA, is boundary with the end plaste externally, wherein can use coolant field along active face.
Selection is used to make up material require balance consideration following parameter, for example gross density (quality and volume), surface contacted resistance, body conductivity and the corrosion-resistant and oxidative resistance of end plaste 10.Therefore the aspect of end plaste material require important consideration comprises intrinsic surface conductivity and the body conductivity of material as the current-collector of conductive region, prevents any etching condition at nonconducting fluid transit area simultaneously.Material in the past comprises lightweight metal, comprises titanium or aluminium.Owing to have high intrinsic body conductivity, low sheet resistance and relative light weight, aluminium is the specially suitable material that is used in the end plaste.But at H
2-O
2/ air PEM fuel cell in service, in electroactive or conduction contact zone, aluminium has the tendency of oxidation.This oxidation will form oxide skin(coating) on the surface, thereby not increase sheet resistance with allowing.The invasion and attack that many further lightweight metals are corroded easily are because this kind corrosion susceptibility and oxidation tendency have used different protective coatings.Yet this protective coating often makes the resistance of metallic plate be increased to unacceptable grade, or this protective coating expense costliness, for example adopts gold or platinum coating.Therefore between conductivity and corrosion protection, there is trade-off relation.
According to an aspect of the present invention, can handle the end plaste of making by corrosion susceptible materials 10, make it can be corrosion-resistant and the invasion and attack of oxidation, allow to use for its weight with respect to other metal of corrosion resistant metal more with low surface contacted resistance and higher body conductivity with this.Comprise that these corrosion susceptible materials have increased the total weight efficiency (being per unit mass efficient) of fuel cell pack.
As shown in Figure 2, terminal collector end plate 10 has non-conductive regional 100 and conductive region 102.The conductive region 102 of end plaste 10 usually by sealing gasket 33,35 never conductive region 100 separate (see figure 1).Yet if liner 33,35 was owing to corrosion was lost efficacy, corrosive liquids may be transferred to conductive region 102 and leach aluminium ion.These aluminium ions may be transferred in battery pile and the single fuel cell.Because this aluminium ion occupies the position of catalyst, thus harmful to the catalyst among the MEA, with the decreased performance that makes that battery and entire cell are piled.
The main body of the extend past end plaste 10 in non-conductive regional 100 or the slit of substrate 128 104 allow the transmission of fluid turnover battery pile under service conditions.The different fluid that enters battery pile comprises hydrogen-containing gas, oxygen-containing gas and liquid coolant (for example mixture of ethylene glycol and water).Therefore in first side 106 of end plaste 10, first slit 110 is the anode supply hydrogen-containing gas of at least one MEA from the battery pile outside to battery pile inside from memory or preparation point 48 (see figure 1)s, second slit 112 is the negative electrode supply oxygen-containing gas of at least one MEA to battery pile inside from oxygen memory or bleeding point 46 (see figure 1)s, the 3rd slit 114 to battery pile internal feed liquid coolant, is used to cool off the zone of bipolar plates or contact plate inside, end from memory point 52 (see figure 1)s.
The specific quantity in slit 104 or order only exemplarily are described at this without limits, because a plurality of structures can be approved by those skilled in the art.Bipolar plate flow field design can be stipulated entrance and exit gap structure and fluid supply layout.In a preferred embodiment, first side 106 has towards last collection sheet 120, and its opposite side 108 faces down, so that gravity is to the effect of liquid coolant maximization, thereby helps its to move when cooling agent enters into battery pile inside after.On second side of end plaste 108, Fpir Crevices crack 122 is sent to the outside with the effluent of anode from battery pile inside, the 5th slit 124 is sent to the battery pile outside with the negative electrode effluent, the 6th slit 126 will be cooling agent by inner at least one bipolar plates of battery pile be sent to the battery pile outside.Like this, metal substrate 128 below is exposed in the fluid that enters and discharge battery pile, quickened non-conductive regional 100 corrosion of end plaste 10, particularly be under the mal-condition that appears at battery pile " wet side " (being a side of face inside fuel battery negative pole).Think that further owing to be polarized to high positive voltage when end plaste 10 is exposed in the different gas-pressurizeds, acid attack and oxidation will speed up and impel the corrosion of end plaste 10 substrates, though this theory limiting terminal plate 10 mechanism of corroding not.
According to preferred embodiment of the present invention as shown in Figure 2, with surface 130,132 passivation of non-conductive regional 100 exposure.The passivation that adopt in this place is often referred to handles metal to reduce the process of surface chemical reaction or corrosion tendency.The surface that is exposed in bad or the corrosive atmosphere in the fuel cell is passivated, to form passivation layer 142 on non-conductive regional 100 surface 130,132.A kind of preferred passivating process is that aluminum metal substrate 128 is made anodization.Anodization is being known in the art, is often referred to the conversion process of electrochemical metal coated with the protectiveness film, and this protectiveness film makes plate be the electrochemistry inertia.In a preferred embodiment of the invention, anodization forms the surface metal oxide layer, and for example alumina layer is compared with parent metal-metallic aluminium, and its electrochemically reactive is low significantly.Therefore the corrosion resistance of the metal of passivation is higher significantly.Further, alumina layer is convenient to the coating that better adhesion of subsequent applies.Can minimize the latent defect in the coating like this, the aperture that no metallizing zone is exposed.These apertures originate from that the metal surface is little, unprotected zone, have the potentiality that possibility develops into the corrosion place.These places can be further enlarge on the surface, so the tack of the layer of surface passivation layer by improving corrosion resistance and any subsequent coated, thereby make the appearance of this type of defective minimize.
Many different alumite methods are known in the art.Required protective layer under the service conditions is depended in the characteristic of alloy and the battery in the selection of anodization process.For example, a kind of anodization process is used chromic acid on the aluminium surface, and with the formation aluminium oxide and at " Metals Handbook " 8th Edition, Vol.2p.612 has more detailed description in (American Society forMetals, 1964).According to the anodization method that is adopted, the processing procedure duration that forms passivation layer 95 is not waited from about 5 minutes to surpassing 4 hours.The thickness of the film that is produced then from 5 microns to not waiting greater than 700 microns.In an alternative preferred embodiment, use chemical conversion coating with passivating metallic surfaces, wherein metal is converted into active little kind in the OR chemical reaction.
The conductivity impedance of the conductive region of end plaste to minimize for the power output of keeping fuel cell be important.The passivation layer 142 coated with conductive zones 102 of electrochemistry inertia can reduce the conductivity of the end plaste 10 of fuel battery inside, because conductive region 102 is main guiding paths of the interior electric current that is produced of fuel cell pack.Electric current advances to each bipolar plates or end contact plate (for example conductor fluid distribution member) 8,14,16 from MEA 4,6 (see figure 1)s, then by conducting medium 43,45 incoming terminal collector plate 10,12, to set up the accumulation electromotive force of leap battery pile from an end plaste 10 to relative end plaste 12.The collection sheet 120 of periphery 146 that is arranged in a side 106 of end plaste 10 sends electric currents from the conductive region 102 conducting metal body 128 by end plaste 10 to collecting sheet 120.The cable or wire (not shown) is attached in to be collected on the sheet 120, and the cable or wire of reverse charging is attached on another collection sheet of battery pile opposite side.Conductive region 102 and collection sheet 120 must keep enough surface conductivity like this, to satisfy the normal operation of fuel cell.Passivation layer 142 can make the surface insulate relatively by reducing surface conductivity, yet this does not influence body or intrinsic conductivity through body 128.In a preferred embodiment of the invention; only corrosion-prone non-conductive regional 100 have passivation layer 142 as protective finish 140; its acid and alkali of this coating protection corrodes and oxidation, and still allows electric charge to flow to collecting sheet 120 from conductive region 102 in the body 128 of end plaste 10.
In aspect another of the preferred embodiment of the invention, protective finish 140 comprises the polymer coating 150 that is coated on non-conductive regional 100 surfaces 130,132, sees Fig. 3, and Fig. 3 is along the sectional view of 3-3 ' line among Fig. 2.Non-conductive regional 100 of the surface 130,132 of end plaste 10 can scribble nonconducting polymer.Non-conductive regional 100 sheet resistance of the end plaste 10 that has increased does not influence the conductivity through the body 128 of end plaste 10.Also consider multiple layer polymer coating 150a, 150b,, can be following surface 130,132 better corrosion protection is provided because thickness increases.
Form the polymer of polymer coating 150, or the selection of mixture of polymers is compatible with the metallic substrate surfaces 130,132 of end plaste 10, also will take into account its corrosion resistance.This kind polymer comprises crosslinked arbitrarily or water-insoluble polymer when solidifying, and this polymer can form thin coherent film on the metal substrate 128 below, and this film can tolerate the bad oxidizability and the sour environment of fuel cell.Therefore can use following polymer among the present invention: such as epoxy resin, silicones, polyamidoimide, Polyetherimide, polyphenol, fluorinated elastomer (for example polyvinylidene fluoride), polyester, phenoxy phenoxy phenyl, epoxy phenol, acrylic resin and carbamate etc.Cross-linked polymer is preferably used for making the impermeability of corrosion resistance characteristic coating is provided.
In a preferred embodiment of the invention, only non-conductive regional 102 have protective coating 140.When end plaste 10 is protected, when for example being subjected to passivation protection, conductive region 102 and collect sheet 120 surface-coated lids or apply mask.Mask is to be applied to arbitrarily on the substrate and to keep stable material when passivation and/or polymer apply.This material can comprise the photomask of being made by typical light-proof material.Like this protective coating 140 only battery non-conductive regional 100 on form.Zone along mask 166 edges can have some passivation layers or oxide formation thing, and selectively can clean these zones 166 to remove any oxide that exists by mechanical wear, chemical etching or similar approach.
When end plaste 10 by corrosion susceptible materials, when for example aluminium was made, conductive region 102 may be subjected to oxidizability and corrode, and formed undesirable alumina layer and increased the contact resistance on surface 132.This oxide skin(coating) has reduced the power output and the operational efficiency of battery pile significantly.One aspect of the present invention is to apply conductive region protective coating 156, covers on the conductive region 102 of end plaste 10.
In a preferred embodiment of the invention, conductive region protective coating 156 comprises resistance to oxidation metal 158, and it is better and protective substrate 128 is not oxidized than the oxidation resistance of following substrate metal 128.Resistance to oxidation refers to suppress oxidability can resist the oxidation better material than following metal.Applying metal level 158 can adopt traditional physical vapor deposition (PVD) technology (for example magnetron sputtering) or chemical vapor deposition (CVD) technology to realize that these technology are known for those of ordinary skills.The plating process comprises electrolysis plating and electroless plating, all can be used for applying this type of metal coating.
Before depositing metal layers 158, can remove lip-deep any impurity or the oxide skin(coating) that exists naturally to prepare surperficial 132 by machinery, chemistry or electrochemical mode.Remove natural oxide from whole conductive region 102 substrate surfaces 132 and can guarantee that follow-up oxidation-resistant coating 156 adheres to.One deck resistance to oxidation metal 158, for example platinum, gold, nickel, tin, silver, their alloy, their mixture and their equivalent, keep required surface conductivity, had low relatively contact resistance, prevented to hinder the formation of the oxide skin(coating) of conductivity simultaneously.The metal level 158 that contains nickel is particularly preferred.One preferred aspect in, do not have nickel that electricity applies as the lower floor under the polymer coating of filling particulate.
In being exposed to certain internal stack environments, the oxidation resistant metal layer 158 that covers on the substrate 128 may need further protection, in case the formation of oxidation thing layer.Alternative preferred embodiment of the present invention comprises conductive region protective coating 156, and this coating comprises the conduction oxidation-resistant coating 160 that contains polymer that is applied on the oxidation resistant metal layer 158.In fuel cell operation, by clamping device, the bolt that for example extends through battery pile clamps end plaste 10, so that several stack components presses each other.Normally in service, end plaste 10 conductive regions 102 sealed liners 33,35 are the conductive region physical separation never like this.Yet when being exposed under the corrosivity condition, liner may be degenerated or lose efficacy, and makes that fluid is communicated with between conductive region 102 and non-conductive regional 100.Corrosive liquids on non-conductive regional 100 may move in the conductive region 102.Therefore, by prophylactically being that conductive region 102 substrates 128 apply corrosion-resistant and sludge proof coating 160, such conduction oxidation-resistant coating 160 that contains polymer has prevented that also the aluminium ion that leaches from making the catalyst poisoning in the battery pile.
The conduction oxidation-resistant coating 160 that preferably contains polymer comprises based polyalcohol or polymeric blends, be similar to the aforesaid polymer that is applied to the non-conductive coating 150 on non-conductive regional 100 that is elected to be, but further comprise electrically conductive particles filler 162, to arrive necessary conductivity.The conduction oxidation-resistant coating 160 that contains polymer must conduct electricity, and resistance coefficient is less than about 50ohm-cm usually.Feature according to selected polymer, the conduction oxidation-resistant coating 160 that contains polymer further can optionally comprise resistance to oxidation, be not dissolved in the electrically conductive particles 162 (promptly less than about 50 microns) of acid, and this particulate intersperses among in the oxidation-resistant coating 160 of conductive region.These electrically conductive particles 162 make to have conductivity by conductive region protective coating 156.Corrosion-resistant and the oxidation resistant polymers that contains the filler particulate of multiple conduction is further discussed in the U.S. Patent No. 6,372,376 of authorizing people such as Fronk to some extent.
Electrically conductive particles 162 can be selected from comprise following group: gold, platinum, graphite, carbon, nickel, the metal boride of conduction, nitride and carbide (for example titanium nitride, titanium carbide, titanium boride) contain the titanium alloy of chromium and/or nickel, palladium, niobium, rhodium, rare earth metal and other noble metal.Most preferably, particulate 162 can comprise carbon or graphite (i.e. six side's crystalline carbon).According to the conductive features (determining the degree of required conductivity) of polymer self and further according to the density of particulate 162 and conductivity (promptly have high conductance and low-density particulate can be used for lower percentage by weight), the conduction oxidation-resistant coating 160 that contains polymer comprises the particulate 162 of Different Weight percentage.The conductive coating 160 of carbon containing/graphite can typically contain the carbon/graphite particulate 162 of 25% percentage by weight.
The conduction oxidation-resistant coating (150,160) that contains non-conductive zone and conductive region polymer can adopt many modes to be applied on conductive region 102 substrate surfaces 132, (1) electrophoretic deposition for example, (2) brushing, spraying, trowelling, (3) lamination or (4) powder coated.The powder coated of polymer material 150,160 is particularly preferred, because compare with other polymer applying method, can make the deposition of polymer high efficiency and less wastage, can on the surface that has had polymeric layer in advance, apply, porousness is low, and makes polymer be deposited as thicker layer full and uniformly.Powder coated is being known in the art, and works as the polymer particles of doing and (for example leave injector
Lined or Corona) time apply voltage more than the common 80kV by it, be used to multiple conduction and non-conductive substrate to apply.Multiple polymers can adopt the method to apply, and comprises epoxy resin, polyamide and polyimides without limitation.Powder coated is specially adapted to apply non-conductive regional corrosion-resistant polymeric layer 150, wherein applies two to three polymeric layers, to reach the thickness in approximate about 50 to 250 micrometer ranges.Electrophoretic deposition also is used for electrically-conductive backing plate, and the method that applies cathode loop epoxy resins, acrylic resin, carbamate and polyester efficiently is provided.The baking of the follow-up substrate that has applied can make the crosslinked and sclerosis of the coating that applies by powder coated or electrophoretic deposition.Polymer applying method described herein both be not used on non-conductive regional 100 (promptly the having electrically conductive particles) of end plaste 10 and had applied non-conductive protectiveness polymer coating 150, was used on the conductive region 102 (promptly with electrically conductive particles) of end plaste 10 yet and applied the conduction oxidation-resistant coating 160 that contains polymer.
The alternative method that applies polymer coating (for example 150,160) is at first polymer to be formed discontinuous film (for example by solvent cast method or extrusion molding etc.), then for example by hot roll lamination to the working surface 130,132 of end plaste 10.Discontinuous film preferably contains the processing of plasticizer with the film of improvement in this applying method, and provides coating on substrate 128 tops, and this coating is enough soft to make that film can not be torn or rupture when end plaste 10 further processing.Fluorinated elastomer, for example polyvinylidene fluoride etc. can be used for present embodiment, can with conventional plasticizers, for example dibutyl phthalate uses jointly.
Alternately, by spraying, brushing or trowelling (for example using scraper) polymer film 150,160 is applied on the working surface 130,132 of substrate 128.By polymer dissolution can be formed coating precursor in suitable solvent, selectively, the filler particulate 162 of conduction can mix with dissolved polymers, and is when containing the conduction oxidation-resistant coating 160 of polymer when it, it can be applied to substrate 132 tops as wet pulp.The coating drying that should wet then (promptly remove and desolvate) is also pressed required curing (for example hot curing).When having electrically conductive particles 162, electrically conductive particles will be by the polymer that does not have solvent attached on the substrate 128.
Be applicable to that the preferred polymer that spraying, brushing or trowelling apply comprises polyamide-imides Thermocurable polymer.Polyamide-imides is dissolved in the solvent of the mixture that includes N-methyl pyrrolidone, propylene glycol and methyl ether acetate.Selectively in this solution, add about 21% to the graphite of about 23% percentage by weight and the mixture of carbon black particle, wherein the range scale of graphite particulate is from about 5 microns to about 20 microns, the range scale of carbon black particle is from about 0.5 micron to about 1.5 microns, less carbon black particle is used for being filled into the space between the bigger graphite particulate, compares the conductivity that has increased coating thus with full equadag coating.Mixture is applied on the substrate 128, and drying also is cured to the coating 150,160 that thickness is about 15-30 micron (being preferably about 17 microns), and its carbon-graphite content is about 38% percentage by weight (if selecting for use).Can slowly solidify down in low temperature (promptly less than 400 degrees Fahrenheits), or in the process of two steps, solidify faster, wherein at first removed solvent in ten minutes by heating under the temperature of 300-350 degrees Fahrenheit (promptly dry), heat (500-750 degrees Fahrenheit) a period of time cure polymer then under higher temperature, time remaining length is from about 30 seconds to about 15 minutes (depending on employed temperature).
Preferred processing method comprises along the first type surface 130,132 of pending body 128 selects zone (being non-conductive regional 100).Before the processing, all not selected areas along the first type surface 130,132 of body 128 (being conductive region 102) are being applied mask before applying protective coating 140 for non-conductive regional 100.Protective coating 140 comprises passivation layer 142, optionally further comprises the corrosion-resistant polymeric layer 150 of conduction.Consider optionally treatment step among the embodiment of a replacement of the present invention; wherein end plaste 10 has the polymeric layer 150 of passivation layer 142 and conduction; and be passivated to handle any aperture that may be present in below the protective coating 140, this aperture may provide the place of the corrosion growth on the metal substrate 128.Additional Passivation Treatment will be handled those metals that is positioned at the aperture below that appears on passivation layer 142 or the polymeric layer 150, with this enhanced protection coating 140.After applying protective coating 140 on non-conductive regional 100, remove mask (not drawing) from conductive region 102.New mask is placed on just coated non-conductive regional 100, wherein, protects it not influenced by the processing of follow-up conductive region 102.Conductive region 102 can further carry out preliminary treatment by abrasion or chemical corrosion.Apply conductive region protective coating 156 then on conductive region 102, this protective coating 156 comprises oxidation resistant metal layer 158 and contains the conduction oxidation-resistant coating 160 of polymer.After applying conductive region protective coating 156 on the conductive region 102, never remove mask on the conductive region 100.
The present invention provides the ability that applies corrosion-resistant finishes for the non-conductive zone of the end plaste made by corrosion susceptible materials with this; and further selectively protected conductive region with conductive coating; the problem in the corrosion place that enlarges rapidly on the metal and the problem of undesirable surface conductance partial oxidation have been overcome, these problems otherwise cause stack performance to descend.
Though the present invention discusses according to its specific embodiment, the meaning is to be not limited to this, but the scope that only limits to provide in the following claims.Argumentation of the present invention substantially only is exemplary, and the variation meaning that does not therefore deviate from the invention main idea is in the scope of the invention.This type of changes the spirit and scope of not thinking with invention and deviates from.
Claims (38)
1. conductive terminal plate, it comprises
First body made of corrosion susceptible materials by conduction;
The first surface of described first body, it has conductive region and non-conductive zone;
Cover the anti-corrosion layer in described non-conductive zone; And
Electrically contact with the first of described first body first, described first is positioned at below the described non-conductive zone and from the conductive path of described conductive region through described first to the first slice.
2. central authorities and described non-conductive zone that end plaste according to claim 1, wherein said conductive region are positioned at described first surface center on described middle section.
3. end plaste according to claim 1, wherein said anti-corrosion layer comprises passivation layer.
4. end plaste according to claim 1, wherein said anti-corrosion layer comprises non-conductive polymer coating.
5. end plaste according to claim 1, wherein said anti-corrosion layer comprise passivation layer and non-conductive polymer coating.
6. end plaste according to claim 5, wherein said polymer coating comprises the polymer that at least one is selected from following polymers: epoxy resin, silicones, polyamidoimide, Polyetherimide, polyphenol, fluorinated elastomer, polyester, phenoxy phenoxy phenyl, epoxy phenol, acrylic resin and carbamate.
7. end plaste according to claim 1, wherein end plaste has at least one slit by described first, and wherein said slit has the surface that is coated with described anti-corrosion layer.
8. end plaste according to claim 7, the described anti-corrosion layer in the anti-corrosion layer in wherein said slit and described non-conductive zone is continuous.
9. end plaste according to claim 1, wherein said first body comprises aluminium.
10. end plaste according to claim 1; wherein said conductive region is coated with protective coating; this coating comprises the ground floor that includes the resistance to oxidation metal that contacts with the surface of described conductive region; with the second layer on the described ground floor, the described second layer comprises oxidation resistant polymers.
11. end plaste according to claim 10, wherein said resistance to oxidation metal comprise the combination of alloy or first group of metal of a kind of metal in first group of metal, first group of metal, wherein, this first group of metal is made up of nickel, tin and silver.
12. end plaste according to claim 10, the wherein said second layer further comprises the electrically conductive particles that is dispersed in the described oxidation resistant polymers.
13. end plaste according to claim 12, wherein said electrically conductive particles is selected from following particulate: gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
14. end plaste according to claim 10, wherein said oxidation resistant polymers is selected from following polymers: epoxy resin, silicones, polyamidoimide, Polyetherimide, polyphenol, fluorinated elastomer, polyester, phenoxy phenoxy phenyl, epoxy phenol, acrylic resin and carbamate.
15. end plaste that is used for collecting the electric current of the one or more electrochemical cells generations that stride across battery pile, each battery comprises the membrane electrode assembly between the pair of conductive fluid distributing element that is clipped in a plurality of conductor fluid distribution members in the battery pile, wherein set up from the electrically contacting of membrane electrode assembly through these a plurality of conductor fluid distribution members, wherein electrically contact apart from the end plaste nearest first conductor fluid distribution member and end plaste, described end plaste comprises:
By first body that conducts electricity and corrosion-prone material is made; And
The surface of described first body, it has conductive region that contacts with the described first conductor fluid distribution member and the non-conductive zone that is covered by anti-corrosion layer;
Wherein said conductive region is positioned at described end plaste surface central authorities and described non-conductive zone around described middle section and define the peripheral non-conductive zone of plate, make thus plate from around environment electric insulation;
Electrically contact with the first of described first body first, described first is positioned at below, described non-conductive zone, and from the conductive path of described conductive region through described first to the first slice.
16. end plaste according to claim 15, wherein end plaste has at least one slit by described first, wherein said slit is communicated with these a plurality of conductor fluid distribution member fluids, and described slit has the surface that is coated with described anti-corrosion layer.
17. end plaste according to claim 15, wherein said anti-corrosion layer comprises passivation layer.
18. end plaste according to claim 15, wherein said anti-corrosion layer comprises non-conductive polymer coating.
19. end plaste according to claim 15, wherein said anti-corrosion layer comprise passivation layer and non-conductive polymer coating.
20. end plaste according to claim 19, wherein said polymer coating comprises the polymer that at least one is selected from following polymers: epoxy resin, silicones, polyamidoimide, Polyetherimide, polyphenol, fluorinated elastomer, polyester, phenoxy phenoxy phenyl, epoxy phenol, acrylic resin and carbamate.
21. end plaste according to claim 16, the described anti-corrosion layer in the anti-corrosion layer in wherein said slit and described non-conductive zone is continuous.
22. end plaste according to claim 15, wherein said first body comprises aluminium.
23. end plaste according to claim 15; wherein said conductive region is coated with protective layer; this layer comprises the ground floor that includes the resistance to oxidation metal that contacts with the surface of described conductive region and the second layer on the described ground floor, and the described second layer comprises oxidation resistant polymers.
24. end plaste according to claim 23, wherein said resistance to oxidation metal comprise the combination of alloy or first group of metal of a kind of metal in first group of metal, first group of metal, wherein, this first group of metal is made up of nickel, tin and silver.
25. end plaste according to claim 23, the wherein said second layer further comprises the electrically conductive particles that is dispersed in the described oxidation resistant polymers.
26. end plaste according to claim 25, wherein said electrically conductive particles is selected from following particulate: gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
27. end plaste according to claim 23, wherein said oxidation resistant polymers is selected from following polymers: epoxy resin, silicones, polyamidoimide, Polyetherimide, polyphenol, fluorinated elastomer, polyester, phenoxy phenoxy phenyl, epoxy phenol, acrylic resin and carbamate.
28. a method that forms the conductive terminal plate, it comprises:
First body that provides electric conducting material to make with main surface;
In the selection area on described main surface, form at least one slit by described first body;
The described selection area of passivation forms nonconducting corrosion-resistant surface thus in described selection area; And
Provide that first with described first body electrically contacts first and from the conductive path of described electric conducting material through described first to the first slice, described first is positioned at below the described non-conductive corrosion-resistant surface.
29. according to the method for claim 28, further comprise coating step after described passivation step, wherein said selection area is coated with corrosion resistant polymeric layer.
30. method according to claim 29; further behind described coating step, comprise the protection step; wherein passivation is carried out in each zone with aperture of described corrosion resistant polymeric layer, handled the aperture that each is positioned at the below thus, described aperture exposes the surface of aperture below.
31., further be included in the step that described slit forms after the step and the non-selected zone on described main surface applied mask before described passivation step according to the method for claim 28.
32., further may further comprise the steps after applying masks described according to the method for claim 31:
Remove described mask from the described non-selected zone on described main surface;
Described selection area to described main surface applies mask; And
Oxidation resistant layer for described non-selected regional coated with conductive.
33. end plaste according to claim 12, wherein said electrically conductive particles is the compound of the composition selected from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
34. end plaste according to claim 12, wherein said electrically conductive particles is the alloy of the composition selected from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
35. end plaste according to claim 12, the mixture of ingredients of wherein said electrically conductive particles for from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon, selecting.
36. end plaste according to claim 25, wherein said electrically conductive particles is the compound of the composition selected from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
37. end plaste according to claim 25, wherein said electrically conductive particles is the alloy of the composition selected from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon.
38. end plaste according to claim 25, the mixture of ingredients of wherein said electrically conductive particles for from gold, platinum, nickel, palladium, rhodium, niobium, titanium, chromium, rare earth metal and carbon, selecting.
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|---|---|---|---|
| US10/358,697 | 2003-02-05 | ||
| US10/358,697 US6793544B2 (en) | 2003-02-05 | 2003-02-05 | Corrosion resistant fuel cell terminal plates |
| PCT/US2004/002959 WO2004073086A2 (en) | 2003-02-05 | 2004-02-03 | Corrosion resistant fuel cell terminal plates |
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| CN1826710A CN1826710A (en) | 2006-08-30 |
| CN1826710B true CN1826710B (en) | 2010-04-28 |
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| CN2004800035927A Expired - Lifetime CN1826710B (en) | 2003-02-05 | 2004-02-03 | Corrosion resistant fuel cell terminal plates |
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| US (1) | US6793544B2 (en) |
| JP (1) | JP2006516796A (en) |
| CN (1) | CN1826710B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2004073086B1 (en) | 2005-10-20 |
| DE112004000171T5 (en) | 2008-01-10 |
| US20040151952A1 (en) | 2004-08-05 |
| WO2004073086A3 (en) | 2005-09-15 |
| WO2004073086A2 (en) | 2004-08-26 |
| DE112004000171B4 (en) | 2014-05-08 |
| JP2006516796A (en) | 2006-07-06 |
| US6793544B2 (en) | 2004-09-21 |
| CN1826710A (en) | 2006-08-30 |
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